Polymerizable compound, polymer compound and block polymer compound, and composition, image-forming method and image-forming apparatus using the same

ABSTRACT

A composition containing a polymer compound and medium being a solvent or a binder resin, wherein the polymer compound comprises monomer units represented by the general formula (1):  
                 
wherein A is a straight-chain or branched alkylene group of 1 to 15 carbon atoms, which may be substituted; m is an integer of 0 to 30, and; B is a single bond or alkylene, which may be substituted; D is an aromatic ring structure; n is an integer of 1 to 10, and R is a hydrogen atom, an alkyl group, which may be substituted, an aromatic ring structure, or a mono- or poly-valent metal cation.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel polymerizable compounds, polymercompounds and block polymer compounds useful as various functionalmaterials. The present invention also relates to compositions using thesame, as well as image-forming methods and image-forming apparatusesusing the same. Specifically, the present invention relates to recordingmaterials using the above compound with a solvent or dispersion medium,ink compositions or toner compositions using the above compound with acolorant, as well as various image-forming methods and apparatuses usingsuch compositions.

2. Related Background Art

Various ink or toner compositions have been prepared dissolving ordispersing a colorant in a medium, and for this purpose, various polymercompounds have been preferably used such as styryl, acrylic andmethacrylic polymers. In production of solvent- or water-based colorantcompositions, improvement of dispersibility of the colorant, e.g.,pigment, has been tried using a polymer compound preferably those havingan ionic functional group.

Meanwhile, polymer compounds having a polyvinyl ether main chain areknown to be polymer materials having a flexible polymer chain.Heretofore, however, few attempts have been made to incorporate an ionicfunctional group to the monomer unit of a polymer compound. Only thefollowing documents 1 and 2 describe several carboxylic acids and estersthereof as potential compounds for this purpose. At present, morestability is required for such a compound, as well as higherdispersibility and stability in a composition.

-   1. Journal of Polymer Science, Part A, Polymer chemistry, vol. 27,    pp. 3303 to 3314 (1989)-   2. Pure Applied Chemistry, Vol. A36, No. 3, pp. 449 to 460 (1999)

SUMMARY OF THE INVENTION

The present invention was made in consideration of the above conditions.The inventors of the present invention made this invention after theextensive study of the conventional techniques and problems involvedtherein.

The following patent documents 1 to 12 are incorporated herein fordescribing the present invention:

-   1. U.S. Pat. No. 4,723,129-   2. U.S. Pat. No. 4,740,796-   3. U.S. Pat. No. 4,463,359-   4. U.S. Pat. No. 4,345,262-   5. U.S. Pat. No. 4,313,124-   6. U.S. Pat. No. 4,558,333-   7. U.S. Pat. No. 4,459,600-   8. Japanese Patent Application Laid-Open No. 59-123670-   9. Japanese Patent Application Laid-Open No. 59-138461-   10. Japanese Patent Application Laid-Open No. 11-080221-   11. Japanese Patent Application Laid-Open No. 11-322942-   12. Japanese Patent Application Laid-Open No. 11-322866.

One object of the present invention is to provide a polymer compound anda block polymer compound suitable for achieving good dispersibility of acolorant or a solid for ink and toner compositions.

Another object of the present invention is to provide a stable, novelpolymerizable compound to produce the above polymer compound.

Still another object of the present invention is to provide animage-forming method and image forming apparatus that use a recordingmaterial such as ink and toner composition containing the above polymercompound.

According to the first aspect of the present invention, there isprovided a composition that comprises a polymer compound and a mediumbeing a solvent or a binder resin, the polymer compound comprising amonomer unit represented by the general formula (1):

wherein A is a straight-chain or branched alkylene group of 1 to 15carbon atoms with or without substitution; m is an integer of 0 to 30,and when m is 2 or more, A is the same or different each other; B is asingle bond or an alkylene with or without substitution; D is anaromatic ring structure; n is an integer of 1 to 10, and when n is 2 ormore, D is the same or different with each other; and R is a hydrogenatom, an alkyl group with or without substitution, or an aromatic ringstructure with or without substitution

According to the second aspect of the present invention, there isprovided a composition comprising a medium being a solvent or a binderresin, and a monomer unit represented by the general formula (2)

wherein A is a straight-chain or branched alkylene group of 1 to 15carbon atoms with or without substitution; m is an integer of 0 to 30,and when m is 2 or more, A is the same or different from each other; Bis a single bond or alkylene with or without substitution; D is anaromatic ring structure; n is an integer of 1 to 10, and when n is 2 ormore, D is the same or different from each other; and M is a mono- orpoly-valent metal cation.

The polymer compound comprising monomer units represented by the generalformula (1) or (2) is preferably a block polymer compound, and the blockpolymer compound having a block structure of monomer units representedby the general formula (1) or (2) is preferably amphipathic.

In relation to the first and second aspects, there is provided acomposition comprising a block polymer compound and a solvent or abinder resin, wherein the block polymer compound has a main chain ofpolyvinyl ether and comprises monomer units of an organic acid of whichpKa is 4.50 or less or a salt thereof.

In relation to the first and second aspects, there is provided acomposition comprising a block polymer, a solvent or binder resin and acolorant, wherein the block polymer comprises at least one monomer unitselected from the group consisting of carboxylic acid ester, carboxylicacid and carboxylic acid salt.

The third aspect of the present invention is a recording materialcomprising a composition described above.

According to the present invention, the recording material is a tonercomposition comprising a binder resin, a colorant, and a polymercompound or block polymer compound comprising monomer units representedby the general formula (1) or (2); or an ink composition comprising asolvent, a colorant, and a polymer compound or block polymer compoundcomprising monomer units represented by the general formula (1) or (2).

In relation to the third aspect of the present invention, there isprovided a recording method comprising a step of thickening the abovecomposition by contacting the composition to hydrogen ions or metalcations.

The present invention also provides an image-forming methodcharacterized in that the above ink composition is deposited by ink-jetrecording on a recording medium.

According to the fourth aspect of the present invention, there isprovided a polymerizable compound represented by the general formula(3):CH₂═CHO(AO)_(m)B(D)_(n)COORwherein A is a straight-chain or branched alkylene group of 1 to 15carbon atoms with or without substitution; m is an integer of 0 to 30,and when m is 2 or more, A is the same or different from each other; Bis a single bond or alkylene with or without substitution; D is anaromatic ring structure; n is an integer of 2 to 10, and D is the sameor different from each other; and R is a hydrogen atom, an alkyl groupwith or without substitution, or an aromatic ring structure with orwithout substitution.

According to the fifth aspect of the present invention, there isprovided a polymer compound comprising a monomer unit represented by thegeneral formula (4):

wherein A is a straight-chain or branched alkylene group of 1 to 15carbon atoms with or without substitution; m is an integer of 0 to 30,and when m is 2 or more, A is the same or different from each other; Bis a single bond or alkylene with or without substitution; D is anaromatic ring structure; n is an integer of 2 to 10, and D is the sameor different from each other; and R is a hydrogen atom, an alkyl groupwith or without substitution, or an aromatic ring structure with orwithout substitution.

According to the sixth aspect of the present invention, there isprovided a polymer compound comprising monomer units represented by thegeneral formula (5):

wherein A is a straight-chain or branched alkylene group of 1 to 15carbon atoms with or without substitution; m is an integer of 0 to 30,and when m is 2 or more, A is the same or different from each other; Bis a single bond or alkylene with or without substitution; D is anaromatic ring structure; n is an integer of 2 to 10, and D is the sameor different from each other; and M is a mono- or poly-valent metalcation.

According to the seventh aspect of the present invention, there isprovided a block polymer compound comprising monomer units representedby the general formula (1).

According to the eighth aspect of the present invention, there isprovided a block polymer compound comprising monomer units representedby the general formula (2).

The block polymer compound comprising monomer units represented by thegeneral formula (1) or (2) is preferably amphipathic.

According to the ninth aspect of the present invention, there isprovided a block polymer compound having a main chain of polyvinyl etherand comprising organic acid monomer units having pKa of 4.50 or less orsalt thereof. The present invention provides a block polymer compound ofpolyvinyl ether structure, wherein at least one type of monomer unitselected from the group consisting of a carboxylic acid ester,carboxylic acid or carboxyl acid salt is present in the monomer units.Block polymer of the present invention is also called block copolymer.

BRIEF DESCRIPTION OF THE DRAWING

FIGURE is a block diagram illustrating a structure of an ink-jetrecording apparatus.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention will be described in detail below.

<Polymer Compound Contained in the First Aspect of the PresentInvention>

The polymer compound to be contained in the composition of the firstaspect of the present invention, comprising monomer units represented bythe general formula (1), is described in detail.

More specifically, the monomer unit represented by the general formula(1) includes:

wherein Ph is 1,4-phenylene or 1,3-phenylene; Py is 2,5-pirimidylene;2,5-Pyr is pyridylene; and Np is 2,6-naphthylene, 1,4-naphthylene or1,5-naphthylene.

In the general formula (1), preferably A is an alkylene group preferablyof a carbon number of 2 to 10, and may be substituted with methyl,ethyl, propyl, phenyl or the like;

m is an integer preferably of 1 to 10;

B is methylene, ethylene, propylene, butylenes, pentylene, hexylene,heptylene, octylene or the like; D is phenylene, pyridylene,pirimidylene, naphthylene, anthranylene, phenanthranylene,thiophenylene, furanylene or the like;

n is an integer of 1 to 5; and

R is an alkyl group of a carbon number of 1 to 10, or an aromatic ringsuch as phenyl, pyridyl, biphenyl group or the like which may besubstituted with an alkyl, alkoxy group, or the like.

The repeating monomer unit represented by the general formula (1) ismore preferably the one represented by the general formula (6):

wherein A is ethylene or propylene; m is an integer of 0 to 5, and whenm is 2 or more, A may be different with each other; B is a single bondor alkylene of 1 to 5 carbon atoms; D is phenylene or naphthylene; n isan integer of 1 to 5, and when n is 2 or more, D may be different ateach occurrence; and R is hydrogen, alkyl or phenyl.

The monomer unit represented by the general formula (1) has a side chainbeing an aromatic carboxylic acid derivative. Since aromatic carboxylicacid derivatives are different from aliphatic carboxylic acidderivatives in acidity, the above monomer structure is very usefulbecause it can provide various functional compositions containingpolyvinyl ether polymer materials of different acidity.

The polymer compound comprising monomer units represented by the generalformula (1) can be obtained by polymerization of a vinyl ether compoundhaving a corresponding substituent. Usually, polymerization is carriedout by cationic polymerization. As a polymerization initiator, protonicacids such as hydrochloric, sulfuric, methanesulfonic, trifluoroacetic,trifluoromethanesulfonic and perchloric acid; Lewis acids such as BF₃,AlCl₃, TiCl₄, SnCl₄, FeCl₃, RAlCl₂ or R_(1.5)AlCl_(1.5), where R is analkyl, in combination with a cation source such as protonic acid, water,alcohol or adduct of vinyl ether and carboxylic acid. The polymercompound can be produced by polymerization of a vinyl ether compound inthe presence of such a polymerization initiator.

The polymer compound comprising monomer units represented by the generalformula (1) has a number-average molecular weight of 200 to 10,000,000,preferably 1000 to 1,000,000. Those having a molecular weight above10,000,000 may not be readily dispersed in a solvent, because ofexcessive entanglement within or between the polymer chains, and thoseof a molecular weight below 200 may not exhibit full steric effect of apolymer compound due to too small molecular weight. The polymer compoundof the present invention may be a homopolymer comprising a singlemonomer unit or copolymer comprising two or more monomer units. In thecase of copolymer, it contains a monomer unit represented by the generalformula (1) preferably at 1% by mole or more, more preferably 3% by moleor more. When the content of the monomer unit represented by the generalformula (1) is lower than 1% by mole, functions such as dispersionimprovement may not be satisfactorily exhibited. Preferably, thecopolymer contains vinyl ether monomer units 50% by mole or more of themonomer units, more preferably 80% by mole or more.

<Polymer Compound Contained in the Second Aspect of the PresentInvention>

A polymer compound to be contained in the second aspect of the presentinvention, which comprises monomer units represented by the generalformula (2), is described in detail.

Specific examples of the monomer units represented by the generalformula (2) include:

wherein Ph is 1,4-phenylene or 1,3-phenylene; Py is 2,5-pirimidylene;2,5-Pyr is pyridylene; and Np is 2,6-naphthylene, 1,4-naphthylene or1,5-naphthylene.

Preferably, in the general formula (2), the alkylene group representedby A has a carbon number of 2 to 10, and may be substituted with methyl,ethyl, propyl, phenyl or the like;

m is an integer preferably of 1 to 10;

B is methylene, ethylene, propylene, butylenes, pentylene, hexylene,heptylene, octylene or the like;

D is phenylene, pyridylene, pirimidylene, naphthylene, anthranylene,phenanthranylene, thiophenylene, furanylene or the like;

n is an integer preferably of 1 to 5; and

M is a monovalent metal cation such as sodium, potassium or lithium, ora polyvalent metal cation such as magnesium, calcium, nickel and iron.When M is a polyvalent metal cation, it forms an ion pair with 2 or moreCOO⁻ anions.

The repeating monomer unit represented by the general formula (2) ismore preferably the one represented by the general formula (7):

wherein A is ethylene or propylene; m is an integer of 0 to 5, and whenm is 2 or more, A may be different each other; B is a single bond oralkylene of 1 to 5 carbon atoms; D is phenylene or naphthylene; n is aninteger of 1 to 5, and when n is 2 or more, D may be different at eachoccurrence; and M is a mono- or poly-valent metal cation.

The polymer compound comprising monomer units represented by the generalformula (2) can be produced by alkaline hydrolysis of the side chainester segment of a polymer compound comprising the corresponding monomerunits represented by the general formula (1). It may be also produced byacid hydrolysis followed by alkali treatment. However, the formerprocess is preferable.

The polymer compound comprising monomer units represented by the generalformula (2) has a number-average molecular weight of 200 to 10,000,000,preferably 1000 to 1,000,000. Those having a molecular weight above10,000,000 may not be readily dispersed in a solvent, because ofexcessive entanglement within or between the polymer chains, and thoseof a molecular weight below 200 may not exhibit full steric effect of apolymer compound due to too small molecular weight. The polymer compoundof the present invention may be a homopolymer comprising a singlemonomer unit or copolymer comprising two or more monomer units. In thecase of copolymer, it contains a monomer unit represented by the generalformula (2) preferably at 1% by mole or more, more preferably 3% by moleor more. When the content of the monomer unit represented by the generalformula (2) is lower than 1% by mole, functions such as dispersionimprovement may not be satisfactorily exhibited. Preferably, thecopolymer contains vinyl ether monomer units 50% by mole or more of themonomer units, more preferably 80% by mole or more.

<Compositions of the First and Second Aspects>

The composition of the present invention comprises a polymer compoundcomprised of monomer units represented by the general formula (1) or(2), and a solvent or a binder resin.

The composition of the present invention preferably further contains apolymer compound, a colorant or a functional material having an intendedfunction, where the polymer compound works to disperse the colorant orthe functional material. The colorant or functional material ispreferably granular solid. Such granular solid useful for the presentinvention includes pigments, metals, herbicides, insecticides,biomaterials and medicine.

The functional material for the composition of the invention may be thepolymer compound of the present invention per se, or may be anothercompound. It is preferably incorporated normally at 0.1 to 50% by weightof the whole composition of the present invention. It may be a solublematerial, or a dye or molecular catalyst.

The polymer compound having a monomer unit represented by the generalformula (1) or (2) is incorporated preferably at 0.5 to 90% by weight ofthe whole composition of the present invention, more preferably 1 to60%, still more preferably 2 to 50%. It may be insufficient indispersion stability below 0.5%, and may be excessively viscous above70%.

The composition of the present invention also comprises a solvent orbinder resin. A solvent or binder resin is incorporated at 1 to 98% byweight, preferably 10 to 96%, still more preferably 20 to 95% of thecomposition. The dispersion stability of the functional material orpolymer compound may be insufficient when the content of the solvent orbinder resin is below 1%, and function thereof may not fully exhibitwhen its function the content of the solvent or binder resin is higherthan 98%.

<Block Polymer Compound>

The polymer compound comprising a monomer unit represented by thegeneral formula (1) or (2) is preferably a block compound.

Amphipathic property is one of the favorable properties of such a blockpolymer compound. This property can be realized when a compound has ahydrophobic and hydrophilic block segments simultaneously. The blockpolymer compound of the present invention can form micelles in anaqueous solvent, when it is amphipathic. Such an amphipathic, polymercompound can make a recording material of favorable properties, asdescribed later.

In general, when a polymer is used to improve dispersion stability andinclusion properties of a functional material, it is preferable that thepolymer is more flexible in molecular motion, because it can physicallyentwine the functional material surface to increase affinity. Moreover,flexibility is preferred due to easy formation of a coating layer on arecording medium, which is discussed later. For this reason, the mainchain of the block polymer preferably has a glass transition temperatureTg of 20° C. or lower, more preferably 0° C. or lower, still morepreferably −20° C. or lower. Satisfactorily, polymers of polyvinyl etherstructure possess a low glass transition temperature and flexiblecharacteristics. Most of the above monomer units have a glass transitiontemperature of around −20° C. or lower.

The composition of the present invention comprises the polymer compound,a colorant or functional material having an intended function, where theblock polymer compound works to disperse the colorant or functionalmaterial. The colorant or functional material can be liquid or solidincluding a soluble material, oil, pigment, metal, herbicide,insecticide, biomaterial, medicine, dye and molecular catalyst.

Another aspect of the present invention is a composition comprising ablock polymer, a solvent or dispersion medium, and a colorant, whereinthe block polymer has a polyvinyl ether monomer unit selected from thegroup consisting of a carboxylate ester, carboxylic acid or carboxylate.The monomer unit of carboxylate ester, carboxylic acid or carboxylate ispreferably represented by the general formula (1) or (2), although notlimited thereto.

The other structural examples include:

A functional material for the composition of the present invention isincorporated at 0.01 to 90% by weight of the composition of the presentcomposition, preferably 0.1 to 50%.

In the composition of the present invention, the block copolymercomprising monomer units represented by the general formula (1) or (2)is contained at 0.2 to 99% by weight of the composition, preferably 0.5to 70%. This content holds also for the block polymer compound having amonomer unit of carboxylate ester, carboxylic acid or carboxylate.

<Recording Material of the Third Aspect of the Present Invention>

The third aspect of the present invention is a recording materialcontaining a composition comprising the polymer compound, solvent ordispersion medium, and colorant.

Specific examples of the recording material are a toner compositioncomprising a dispersion medium (e.g., binder resin), a colorant and apolymer compound, and an ink composition comprising a solvent, acolorant and a polymer compound, wherein the polymer compound comprisesthe monomer units represented by the general formula (1) or (2).

[Ink Composition]

First, the ink composition being one of the preferred embodiments of thepresent invention is described.

The content of the polymer compound comprising monomer units representedby the general formula (1) or (2) is 0.1 to 90% by weight, preferably 1to 80%, of the ink composition. The content is preferably 1 to 30% byweight, when used for ink-jet printing.

Components of the ink composition other than the polymer compound aredescribed in detail below including water, aqueous solvent, colorant andadditives.

[Water]

Water is preferably ion-exchanged water, pure water or superpure waterfrom which metal ions etc. have been removed.

[Aqueous Solvent]

The aqueous solvent useful for the present invention includes polyhydricalcohols such as ethylene glycol, diethylene glycol, triethylene glycol,polyethylene glycol, propylene glycol, polypropylene glycol andglycerin; polyhydric alcohol ethers such as ethylene glycol monomethylether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,diethylene glycol monoethyl ether and diethylene glycol monobutyl ether;and nitrogen-containing solvents such as N-methyl pyrrolidone,substituted pyrrolidone and triethanolamine. Monohydric alcohol such asmethanol, ethanol and isopropyl alcohol can be used to accelerate dryingof the ink on the recording medium.

Water and aqueous solvent are incorporated preferably at 20 to 95%, morepreferably 30 to 90%, by weight of the ink composition of the presentinvention. Organic solvent such as toluene, ethyl acetate, acetone ormethylethylketone may be incorporated in place of water and aqueoussolvent.

[Colorant]

The ink composition of the present invention also contains a colorantsuch as pigment and dye, preferably pigment. Specific examples ofpigment and dye useful for the present invention are described below.

Pigment can be either organic or inorganic. Pigments preferably used forink are pigments of black and three primary colors of cyan, magenta andyellow. Also, other pigments, e.g., pigments of other colors, colorlessor pale colored pigments, pigments of metal luster may be used. Newpigments synthesized for the present invention may be also used.

Followings are examples of commercially available pigments of black,cyan, magenta, and yellow.

Examples of black pigments include, but not limited to, Raven 1060,Raven 1080, Raven 1170, Raven 1200, Raven 1250, Raven 1255, Raven 1500,Raven 2000, Raven 3500, Raven 5250, Raven 5750, Raven 7000, Raven 5000ULTRA II, Raven 1190 ULTRA II (all of the above, manufactured byColumbian Carbon Co.), Black Pearls L, MOGUL-L, Regal 400R, Regal 660R,Regal 330R, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch1300, Monarch 1400 (all of the above, manufactured by CABOTCORPORATION), Color Black FW1, Color Black FW2, Color Black FW200, ColorBlack 18, Color Black S160, Color Black S170, Special Black 4, SpecialBlack 4A, Special Black 6, Printex 35, Printex U, Printex 140U, PrintexV, Printex 140V (all of the above, manufactured by Degussa AG), No. 25,No. 33, No. 40, No. 47, No. 52, No. 900, No. 2300, MCF-88, MA600, MA7,MA8, MA100 (all of the above, manufactured by MITSUBISHI CHEMICALCORPORATION).

Examples of cyan pigments include, but not limited to, C.I. PigmentBlue-1, C.I. Pigment Blue-2, C.I. Pigment Blue-3, C.I. Pigment Blue-15,C.I. Pigment Blue-15:2, C.I. Pigment Blue-15:3, C.I. Pigment Blue-15:4,C.I. Pigment Blue-16, C.I. Pigment Blue-22, C.I. Pigment Blue-60.

Examples of magenta pigments include, but not limited to, C.I. PigmentRed-5, C.I. Pigment Red-7, C.I. Pigment Red-12, C.I. Pigment Red-48,C.I. Pigment Red-48:1, C.I. Pigment Red-57, C.I. Pigment Red-112, C.I.Pigment Red-122, C.I. Pigment Red-123, C.I. Pigment Red-146, C.I.Pigment Red-168, C.I. Pigment Red-184, C.I. Pigment Red-202, C.I.Pigment Red-207.

Examples of yellow-pigments include, but not limited to, C.I. PigmentYellow-12, C.I. Pigment Yellow-13, C.I. Pigment Yellow-14, C.I. PigmentYellow-16, C.I. Pigment Yellow-17, C.I. Pigment Yellow-74, C.I. PigmentYellow-83, C.I. Pigment Yellow-93, C.I. Pigment Yellow-95, C.I. PigmentYellow-97, C.I. Pigment Yellow-98, C.I. Pigment Yellow-114, C.I. PigmentYellow-128, C.I. Pigment Yellow-129, C.I. Pigment Yellow-151, C.I.Pigment Yellow-154.

The composition of the present invention may also contain aself-dispersing pigment dispersible in water. Such pigments fall intotwo types, those covered with adsorbed polymer for steric hindranceeffect, and those utilizing electrostatic repulsion effect. Thecommercial products include CAB-O-JET200 and CAB-O-JET300 (CabotCorporation), and Microjet Black CW-1 (Orient Chemical Industries).

The pigment for the ink composition of the present invention isincorporated preferably at 0.1 to 50% by weight of the ink composition.Content lower than 0.1% may not give a sufficient image concentration,and content higher than 50% may deteriorate fixation properties of theimage. More preferable content is 0.5 to 30% by weight.

Also dye can be used for the ink composition of the present invention.Dyes useful for the present invention include direct, acidic, basic andreactive dyes, water-soluble dyes for food coloring and insolubledispersion dyes.

For example, oil-soluble dyes may be C.I. Solvent Blue-33, -38, -42,-45, -53, -65, -67, -70, -104, -114, -115, -135; C.I. Solvent Red-25,-31, -86, -92, -97, -118, -132, -160, -186, -187, -219; C.I. SolventYellow-1, -49, -62, -74, -79, -82, -83, -89, -90, -120, -121, -151,-153, -154.

For example, water-soluble dyes may be direct dyes such as C.I. DirectBlack-17, -19, -22, -32, -38, -51, -62, -71, -108, -146, -154; C.I.Direct Yellow-12, -24, -26, -44, -86, -87, -98, -100, -130, -142; C.I.Direct Red, -1, -4, -13, -17, -23, -28, -31, -62, -79, -81, -83, -89,-227, -240, -242, -243; C.I. Direct Blue-6, -22, -25, -71, -78, -86,-90, -106, -199; C.I. Direct Orange-34, -39, -44, -46, -60; C.I. DirectViolet-47, -48; C.I. Direct Brown-109; C.I. Direct Green-59,

acid dyes such as C.I. Acid Black-2, -7, -24, -26, -31, -52, -63, -112,-118, -168, -172, -208; C.I. Acid Yellow-11, -17, -23, -25, -29, -42,-49, -61, -71; C.I. Acid Red-1, -6, -8, -32, -37, -51, -52, -80, -85,-87, -92, -94, -115, -180, -254, -256, -289, -315, -317; C.I. AcidBlue-9, -22, -40, -59, -93, -102, -104, -113, -117, -120, -167, -229,-234, -254: C.I. Acid Orange-7, -19; C.I. Acid Violet-49,

reactive dyes such as C.I. Reactive Black-1, -5, -8, -13, -14, -23, -31,-34, -39; C.I. Reactive Yellow-2, -3, -13, -15, -17, -18, -23, -24, -37,-42, -57, -58, -64, -75, -76, -77, -79, -81, -84, -85, -87, -88, -91,-92, -93, -95, -102, -111, -115, -116, -130, -131, -132, -133, -135,-137, -139, -140, -142, -143, -144, -145, -146, -147, -148, -151, -162,-163; C.I. Reactive Red-3, -13, -16, -21, -22, -23, -24, -29, -31, -33,-35, -45, -49, -55, -63, -85, -106, -109, -111, -112, -113, -114, -118,-126, -128, -130, -131, -141, -151, -170, -171, -174, -176, -177, -183,-184, -186, -187, -188, -190, -193, -194, -195, -196, -200, -201, -202,-204, -206, -218, -221; C.I. Reactive Blue-2, -3, -5, -8, -10, -13, -14,-15, -18, -19, -21, -25, -27, -28, -38, -39, -40, -41, -49, -52, -63,-71, -72, -74, -75, -77, -78, -79, -89, -100, -101, -104, -105, -119,-122, -147, -158, -160, -162, -166, -169, -170, -171, -172, -173, -174,-176, -179, -184, -190, -191, -194, -195, -198, -204, -211, -216, -217;C.I. Reactive Orange-5, -7, -11, -12, -13, -15, -16, -35, -45, -46, -56,-62, -70, -72, -74, -82, -84, -87, -91, -92, -93, -95, -97, -99; C.I.Reactive Violet-1, -4, -5, -6, -22, -24, -33, -36, -38; C.I. ReactiveGreen-5, -8, -12, -15, -19, -23; C.I. Reactive Brown-2, -7, -8, -9, -11,-16, -17, -18, -21, -24, -26, -31, -32, -33,

C.I. Basic Black-2; C.I. Basic Red-1, -2, -9, -12, -13, -14, -27; C.I.Basic Blue-1, -3, -5, -7, -9, -24, -25, -26, -28, -29; C.I. BasicViolet-7, -14, -27; C.I. Food Black-1, -2.

The above-described colorant examples are preferable for the inkcomposition of the present invention. However, the useful ones for thepresent invention are not limited to the above. The content of a dye inthe ink composition of the present invention is preferably 0.1 to 50% byweight of the ink.

[Additives]

The composition of the present invention may contain various additivesor auxiliary agents as required. One of the additives useful for thepresent invention is a dispersion stabilizer, which stably disperses thepigment in the solvent. The composition of the present invention candisperse granular solid such as pigment due to the polyvinyl etherpolymer contained therein. However, it may contain another dispersionstabilizer, when its dispersion capacity is insufficient.

As a dispersion stabilizer which can be added to the composition of thepresent invention, there are resins and surfactants having bothhydrophilic and hydrophobic segments therein. Examples of suchamphiphilic resins include a copolymer of hydrophilic and hydrophobicmonomers.

Hydrophilic monomers useful for the present invention include acrylic,methacrylic, maleic and fumaric acid, the carboxylate monoestersdescribed earlier, vinylsulfonic and styrenesulfonic acid, acrylamide,and methacryloxyethyl phosphate or the like. Hydrophobic monomers usefulfor the present invention include styrene and its derivatives, e.g.,styrene and α-methylstyrene; and vinyl cyclohexane, vinylnaphthalenederivative, acrylate esters and methacrylate esters. Copolymers ofvarious structures, such as random, block or graft copolymers may beused for the present invention. Needless to say, the hydrophilic andhydrophobic monomers useful for the present invention are not limited tothe above.

The surfactant for the present invention may be anionic, nonionic,cationic or ampholytic. The anionic surfactants useful for the presentinvention include fatty acid salts, alkyl sulfate ester salts,alkylarylsulfonic acid salts, alkyldiaryl ether disulfonic acid salts,dialkylsulfosuccinic acid salts, alkyl phosphoric acid salts,naphthalene/formalin sulfonate condensate, polyoxyethylene alkylphosphate ester salts and glycerol borate fatty acid esters. Thenonionic surfactants useful for the present invention includepolyoxyethylene alkyl ether, polyoxyethyleneoxypropylene blockcopolymer, sorbitan/fatty acid ester, glycerin/fatty acid ester,polyoxyethylene/fatty acid ester, polyoxyethylenealkylamine, andfluorine- and silicon-based ones. The cationic surfactants useful forthe present invention include alkylamine salts, quarternary ammoniumsalts, alkyl pirydinium salts and alkyl imidazolium salts. Theampholytic surfactants useful for the present invention include alkylbetaine and alkylamine oxide and phosphatidyl choline. The surfactantsuseful for the present invention are also not limited to the above.

The other additives to the ink composition of the present inventioninclude a pH adjustor for stabilizing the ink and securing stability ofthe ink in a flow path of the recording apparatus, a penetration agentfor accelerating penetration of the ink into the recording medium andthereby accelerating apparent drying of the ink, an antifungal agent toprotect the ink from molds, a chelating agent for sequestering metalions in the ink and preventing metal deposition in the nozzle ordeposition of insolubles in the ink, an antifoaming agent for preventingfoaming of the ink during circulation, migration or production of theink, an antioxidant, a viscosity adjustor, an antistatic agent and a UVabsorber.

The ink composition of the present invention can be produced by mixingand uniformly dissolving or dispersing the above components. Forexample, two or more components are mixed with each other, andpulverized and dispersed by using a sand mill, ball mill, homogenizer ornanomizer to prepare the ink base liquid, whose properties are adjustedwith a solvent or additives.

Next, the toner composition of the present invention is described. Morespecifically, the toner composition comprises a dispersion medium suchas a binder resin, a colorant and a polymer compound comprising monomerunits represented by the general formula (1) or (2).

The polymer compound is incorporated at 0.1 to 50% by weight in thetoner composition of the present invention, preferably 0.5 to 30%.

The polymer compound for the present invention can be used as the binderresin itself, or may be used in combination with a binder resin such asstyrene acrylic resin and polyester resin.

The components other than the polymer compound for the toner compositionof the present invention are described below in detail. These componentsinclude binder resins, colorants (pigment or dye), charge controllingagents, releasing agents, external additives and magnetic powder.

[Other Components for the Toner Composition]

The binder resin useful for the toner composition includes styreneacrylic copolymer, polyester and polycarbonate. Binder resin content ispreferably 10 to 99% by weight. As the colorant, the pigments and dyesdescribed earlier for the ink composition can be also used. It isincorporated preferably at 0.1 to 50% by weight. The charge controllingagents useful for the present invention include metal/azo complexes,triphenylmethane-based dyes, nigrosine and ammonium salts. It isincorporated preferably at 0.1 to 30% by weight. The releasing agentsuseful for the present invention include synthetic wax and natural wax.The external additives useful for the present invention include finelypulverized inorganic materials, e.g., silica, alumina and titana; andfinely pulverized resins, e.g., polyvinylidene fluoride (PVDF) andpolytetrafluoroethylene. The magnetic powders useful for the presentinvention include those of magnetite, hematite and ferrite. The tonercomposition of the present invention can work if not all of thesecomponents are contained, and it may contain other components.

The toner composition of the present invention can be produced by mixingthe above components, melting/kneading them to a uniform mixture, finelypulverizing the mixture by a speed mill or jet mill, and classifying theresulting particles to obtain toner particles of an intended size. Thetoner composition can be produced by mixing the resulting tonerparticles with external additives by a mixer.

The composition of the first or second aspect of the present inventioncan have various uses in addition to the toner or ink compositions. Whenthe composition contains a colorant, the colorant is preferablyencapsulated in a block polymer compound that is characteristically usedin the present invention, in view of suppression of weatherdeterioration of the colorant. In the case of a water-soluble ink, anoil-soluble colorant or colorant particles with hydrophobic surface canbe included in the micelles of the block polymer compound rather easily.

Next, the method for thickening the composition of the present inventionis described. The composition of the first or second aspect of thepresent invention becomes thick in contact with hydrogen ions or metalcations. Typically, a solution of the polymer of the first aspect of thepresent invention and a functional material, which is in a dispersed ormicellar condition in an aqueous solution, is brought into contact withhydrogen ion or polyvalent metal cations such as zinc, aluminum,calcium, barium and nickel to agglomerate the dispersion or dispersedmicellar particles. The thickening method preferably involvesagglomeration of the micellar polymer compound. Since the polymer hasionized carboxylic acid salt etc., the ionic functional groups areneutralized in contact with a sufficient quantity of hydrogen ion ormetal cation, to sharply increase affinity between the micelles togreatly increase viscosity. This method is preferably applicable to anink composition. When an ink composition is applied to fixed on arecording medium, ink thickening can provide excellent fixationproperties. The thickening method is suitably applicable to theimage-forming method and apparatus described below.

The composition of the present invention can be thickened by contactingit to a hydrogen ion or polyvalent metal cation solution, or to a mediumcoated beforehand with hydrogen ion or polyvalent metal cation. Theamount of hydrogen ion or polyvalent metal cation is be contacted oradded is in the range of 0.01 to 100 mole equivalents of the ionic groupof the polymer compound, preferably 0.05 to 50 mole equivalents.

Alternatively, the composition of the present invention may thicken inresponse to stimulation. By applying stimulation in the process of imageformation to increase viscosity, good fixation can be achieved. Thestimulus may be selected from those suitable for image formation, e.g.,temperature, pH, concentration, electromagnetic wave, and a combinationthereof.

Next, the image-forming method and apparatus which use the ink or tonercomposition of the present invention are described.

[Image-Forming Method and Apparatus]

The ink composition of the present invention is applicable to a varietyof image-forming methods, e.g., various printing methods, ink-jet methodand electrophotography, and also to an apparatus with which it can formimages based on the above methods.

The image-forming method of the present invention can produce goodimages by the aid of the composition of the present invention. One ofthe preferred embodiments of the image-forming method of the presentinvention is an ink jet method that discharges the ink composition ofthe present invention from an ink discharge nozzle onto a recordingmedium to form an image thereon. One of the preferred methods is anink-jet method that utilizes thermal energy to discharge ink from thenozzle.

Various types of ink-jet printers can use the composition of the presentinvention. These include a piezo-electric ink-jet type with apiezo-electric apparatus, and thermal ink-jet type, which gives athermal energy to the ink to be foamed.

An ink-jet recording apparatus is outlined by referring to FIG. 1. Itshould be understood that the apparatus shown in FIG. 1 is forillustrating but not for limiting the present invention.

FIG. 1 is a block diagram illustrating the structure of an ink-jetrecording apparatus.

The apparatus shown in FIG. 1 does recording on a recording mediummoving the head. Referring to FIG. 1, the motors 56 and 58 responsiblefor driving the head 70 in the X and Y directions, respectively, arelinked to the CPU 50, which commands all actions in the apparatus, viathe circuits 52 and 54 for driving each motor. The CPU 50 instructs themotors 56 and 58 via the circuits 52 and 54 to drive the head 70 in theX and y directions to a given position on the recording medium.

As shown in FIG. 1, the head-driving circuit 60 is also linked to thehead 70, in addition to the motors 56 and 58 for driving the head in therespective X and Y direction, to drive the head 70 for a given action,e.g., discharging the ink, following the instruction from the CPU 50.The CPU 50 receives information of the head 70 position from the Xencoder 62 and Y encoder 64 responsible for detecting the head position,which are also linked to the CPU 50. A control program is inputted inthe program memory 66. The CPU 50 drives the head 70, based on thecontrol program and position information from the X encoder 62 and Yencoder 64, to a desired position on the recording medium, and instructsthe head to discharge the ink at that position. The apparatus forms adesired image on the recording medium in the above manner. For theimage-forming apparatus which can hold 2 or more types of inks forink-jet, the above procedure is repeated necessary times with each inkto produce a given image on the recording medium.

The head 70 can be also moved after it has discharged the ink asrequired, to a position where a means (not shown) for removing surplusink deposited on the head is provided, to be cleaned by proper wipingmeans. Specific cleaning means may be selected from the conventionalmeans used for the above purpose.

On completion of the above image-forming procedure, the recorded mediumis replaced by a new medium by a recording medium conveying mechanism,which is not shown.

The above embodiment can be modified or varied within scope of thepresent invention. For example, the head 70 is moved in the X and Ydirections in the above embodiment. However, it may be designed to moveonly in X (or Y) direction with the recording medium moving in Y (or X)direction, to form image.

According to the present invention, an ink jet recording head providedwith means (e.g., an electro-thermal converting element or a laser) forgenerating thermal energy to discharge the ink brings the excellenteffect. Such a system can produce precision images. The image qualitycan be further improved when the ink composition of the presentinvention is used in thermal ink jet recording.

The representative structures of and working principles for theapparatus provided with a means for generating thermal energy, e.g., theone described above, are preferably based on the basic principlesdisclosed by, e.g., Patent Documents 1 and 2. These apparatuses areapplicable either to the so-called on-demand or continuous type. Theapparatus of the present invention is particularly effective whenapplied to the on-demand type, because the liquid is securely held, andat least one type of driving signal, which corresponds to the dischargeinformation, is applied to the electro-thermal converting elementpositioned in the flow path to generate thermal energy and increasetemperature rapidly enough to cause at least nuclear boiling. Thisthermal energy causes film boiling on the heater board in the head, onwhich bubbles are formed by the action of heat according to the signalsin one-to-one response. The liquid is discharged from the discharge portby expansion/shrinkage of the foams, to form at least one droplet. Thepulsed driving signal is more preferable, because it immediately causesexpansion/shrinkage of the foams, achieving quicker response fordischarging the liquid. The pulse driving signals described in PatentDocuments 3 or 4 are preferable. More excellent discharge can be doneunder the conditions concerning temperature-increasing rate on theheater described in Patent Document 5.

In addition to the head structure described in above Patent Documentscomprising a discharge orifice, an electro-thermal converting element,and a flow path that is straight or right angle, another structuredisclosed in Patent Document 6 or 7 is also included in the presentinvention where the heater is provided in a curved region. All of thesestructures are within scope of the present invention. Moreover, PatentDocument 8 discloses a structure with two or more electro-thermalconverters and a common slit working as the discharge port for theseconverters. Patent Document 9 discloses a structure provided with anopening for absorbing pressure waves caused by the thermal energy as thedischarge port. These structures are also useful for the presentinvention. In short, the present invention can discharge the inksecurely and efficiently by the head of any structure.

The image-forming apparatus of the present invention can alsoefficiently work, when provided with a full-line type head, which coversthe maximum width of the recording medium. The head structure is notlimited. For example, the maximum width can be covered by a combinationof 2 or more heads, or by a single head.

Moreover, the apparatus of the present invention can also efficientlywork, when provided with a serial type head, a head fixed on theapparatus body, or a chip type head that is exchangeably mounted on theapparatus body and electrically linked to and supplied with the ink fromthe apparatus body.

The apparatus of the present invention may be further provided with ameans for removing liquid droplets. Such an apparatus can realize stillmore favorable discharging effect.

The apparatus of the present invention may have a structure providedwith an auxiliary means. Such a structure is preferable, because it canfurther stabilize the effect of the present invention. The specificexamples of these auxiliary means include a capping means for the head,pressurizing or evacuating means, preheating means of anotherelectro-thermal converting element, a different heating element, or acombination thereof, and a preliminarily discharging means other thanthe ink discharging means.

The apparatus most effective for the present invention is that utilizingfilm boiling as described above.

Each port for the head of the present invention preferably discharges0.1 to 100 picoliters of the ink.

The ink composition of the present invention can be also used for anindirect recording system in which an intermediate transfer medium isprinted with the ink and the image is then transferred to a recordingmedium, e.g., paper. It is also applicable to a recording system whichincludes an intermediate transfer medium for direct printing.

<Polymerizable Compound of the Fourth Aspect>

The fourth aspect of the present invention is a compound represented bythe general formula (3). This compound is described in detail below.

More specifically, the polymerizable compounds represented by thegeneral formula (3) include:

-   CH₂═CHOCH₂CH₂O(CH₂)₄PhPhCOOCH₃-   CH₂═CHO(CH₂CH₂O)₇PhPhCOOCH₃-   CH₂═CHOCH₂CH₂OPyPhCOOCH₃-   CH₂═CHOCH₂CH₂OPyPhCOOC₂H₅-   CH₂═CHO(CH₂CH₂O)₂(CH₂)₂₀ONpPhCOOC₂H₅-   CH₂═CHOCH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂O(CH₂)₂OPhPhCOOC₂H₅-   CH₂═CHOCH₂CH₂CH₂CH₂O(CH₂)₃OPhPhCOOC₂H₅-   CH₂═CHOCH₂CH₂CH₂CH₂O(CH₂)₄OPhPhPhCOOC₂H₅-   CH₂═CHOCH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂O(CH₂)₅OPhPhCOOC₂H₅-   CH₂═CHOCH₂CH₂CH₂CH₂CH₂CH₂O(CH₂)₆OPhNpCOOC₂H₅-   CH₂═CHOCH(CH₃)CH₂O(CH₂)₇OPhPhCOOC₂H₅-   CH₂═CHOCH(CH₃)CH₂O(CH₂)₈OPhPhCOOC₂H₅-   CH₂═CHOCH₂CH(CH₃)O(CH₂)₁₀OPhPhCOOC₂H₅-   CH₂═CHOCH(C₂H₅)CH₂O(CH₂)₁₅OPhPhCOOC₂H₅-   CH₂═CHOCH₂CH(CH₃)O(CH₂)₂₀OPhNpCOOC₂H₅-   CH₂═CHOCH₂CH₂O(CH₂)₂OPhPhCOOPhH-   CH₂═CHOCH₂CH₂O(CH₂)₃OPhPhPhCOOCH₂PhH-   CH₂═CHOCH₂CH₂O(CH₂)₄OPhPhCOOPyrH-   CH₂═CHOCH₂CH₂CH₂CH₂O(CH₂)₅OPyrPhCOOPhH-   CH₂═CHOCH₂CH₂O(CH₂)₆OPhPhCOOPh(OCH₃)-   CH₂═CHO(CH₂CH₂O)₂(CH₂)₇OPhPhPhCOOPh(OCH₃)-   CH₂═CHOCH₂CH₂O(CH₂)₈OPhPhCOOPh(OCH₃)-   CH₂═CHOCH₂CH₂O(CH₂)₁₀OPhPhCOOPh(OCH₃)-   CH₂═CHOCH₂CH₂O(CH₂ )₁₅OPhPhCOOPh(OCH₃)-   CH₂═CHOCH₂CH₂O(CH₂ )₂₀OPhPhCOOPh(OCH₃)    wherein Ph is 1,4-phenylene or 1,3-phenylene; Py is    2,5-pirimidylene; 2,5-Pyr is pyridylene; and Np is 2,6-naphthylene,    1,4-naphthylene or 1,5-naphthylene.

In general formula (3), preferably, A is alkylene of a carbon number of2 to 10 with or without substitution with methyl, ethyl, propyl, phenylor the like;

m is an integer of 1 to 10;

B is an alkylene group being methylene, ethylene, propylene, butylenes,pentylene, hexylene, heptylene, or octylene;

D is phenylene, pyridylene, pirimidylene, naphthylene, anthranylene,phenanthranylene, thiophenylene or furanylene;

n is an integer of 2 to 5;

R is an alkyl group of a carbon number of 1 to 10, or an aromatic ringbeing phenyl, pyridyl, biphenyl group or the like with or withoutsubstitution with an alkyl, alkoxy group, or the like.

The polymerizable compound represented by the general formula (3) ismore preferably the one represented by the general formula (8):CH₂═CHO(AO)_(m)B(D)_(n)COOR  General Formula (8)wherein A is ethylene or propylene; m is an integer of 0 to 5, and whenm is 2 or more, A may be different at each occurrence; B is a singlebond or alkylene of 1 to 5 carbon atoms; D is phenylene or naphthylene;n is an integer of 2 to 5, and D may be different at each occurrence;and R is a hydrogen atom, or an alkyl or phenyl group.

The polymerizable compound represented by the general formula (3) has 2or more aromatic rings in the structure and the end of the side chain isan aromatic carboxylic acid derivative. Such a compound is advantageousin that it has high crystallinity and its purification for precisionpolymerization is relatively easy. Moreover, since aromatic carboxylicacid has an acidity different from that of aliphatic carboxylic acid,this polymerizable compound is very useful to provide a variety offunctional polymer compounds of polyvinyl ether structure with varyingacidity.

The polymerizable compound represented by the general formula (3) istypically synthesized by the etherification described below.

<Polymer Compound of the Fifth Aspect>

The fifth aspect of the present invention is a polymer compoundcomprising monomer units represented by the general formula (4). Thiscompound is described in detail below.

More specifically, the monomer units represented by the general formula(4) include:

wherein Ph is 1,4-phenylene or 1,3-phenylene; Py is 2,5-pirimidylene;2,5-Pyr is pyridylene; and Np is 2,6-naphthylene, 1,4-naphthylene or1,5-naphthylene.

Preferably, in the general formula (4), A is an alkylene group of acarbon number of 2 to 10, with or without substitution with methyl,ethyl, propyl, phenyl or the like;

m is an integer of 1 to 10;

B as an alkylene group being methylene, ethylene, propylene, butylenes,pentylene, hexylene, heptylene, octylene or the like;

D is an aromatic ring being phenylene, pyridylene, pirimidylene,naphthylene, anthranylene, phenanthranylene, thiophenylene, furanyleneor the like;

n is an integer of 2 to 5;

R is an alkyl group of a carbon number of 1 to 10, or an aromatic ringof phenyl, pyridyl, biphenyl group or the like with or withoutsubstitution with an alkyl, alkoxy group, or the like.

The repeating monomer unit represented by the general formula (4) ispreferably the one represented by the general formula (9):

wherein A is ethylene or propylene; m is an integer of 0 to 5, and whenm is 2 or more, A may be different; B is a single bond or alkylene of 1to 5 carbon atoms; D is phenylene or naphthylene; n is an integer of 2to 5, and R is a hydrogen atom, or an alkyl or phenyl group.

The compound of the present invention represented by the general formula(4) has 2 or more aromatic rings in the unit structure and the end ofthe side chain is an aromatic carboxylic acid salt. Aromatic carboxylicacid with 2 or more aromatic rings has an acidity different from that ofan aliphatic carboxylic acid. As a result, the compound is very useful,because it provides a variety of functional polymer compounds of varyingacidity with a vinyl ether monomer unit. Moreover, it can exhibit acharacteristic function based on its self-organizing property becausethe portion of aromatic rings has very high crystallinity and highaffinity with each other.

The polymer compound comprising the monomer units represented by thegeneral formula (4) can be produced preferably by polymerization of thepolymerizable compound represented by the general formula (3). Thisprocess is mainly effected by cationic polymerization in the presence ofa polymerization initiator. The polymerization initiators useful for theabove process include protonic acids, e.g., hydrochloric, sulfuric,methanesulfonic, trifluoroacetic, trifluoromethanesulfonic andperchloric acid; and combinations of Lewis acid (e.g., BF₃, AlCl₃,TiCl₄, SnCl₄, FeCl₃, RAlCl₂ or R_(1.5)AlCl_(1.5), where R is an alkyl)and cation source (e.g., protonic acid and water, alcohol or adduct ofvinyl ether and carboxylic acid). The polymer compound can be producedby the polymerization of the polymerizable compound (monomer)represented by the general formula (3) proceeding in the presence of thepolymerization initiator.

The polymer compound comprising monomer units represented by the generalformula (4) has a number-average molecular weight of 200 to 10,000,000,preferably 1000 to 1,000,000. Those having a molecular weight above10,000,000 may not be readily dispersed in a solvent, because ofexcessive entanglement within or between the polymer chains, and thoseof a molecular weight below 200 may not exhibit full steric effect of apolymer compound due to too small molecular weight. The polymer compoundof the present invention may be a homopolymer comprising a singlemonomer unit or copolymer comprising two or more monomer units. In thecase of copolymer, it contains a monomer unit represented by the generalformula (4) preferably at 1% by mole or more, more preferably 3% by moleor more. When the content of the monomer unit represented by the generalformula (4) is lower than 1% by mole, functions such as dispersionimprovement may not be satisfactorily exhibited. Preferably, thecopolymer contains vinyl ether monomer units 50% by mole or more of themonomer units, more preferably 80% by mole or more.

<Polymer Compound of the Sixth Aspect>

The sixth aspect of the present invention is the polymer compoundcomprising monomer units represented by the general formula (5).

The specific examples of the monomer units represented by the generalformula (5) include:

wherein Ph is 1,4-phenylene or 1,3-phenylene; Py is 2,5-pirimidylene;2,5-Pyr is pyridylene; and Np is 2,6-naphthylene, 1,4-naphthylene or1,5-naphthylene.

Preferably, in the general formula (5), A is an alkylene group of acarbon number of 2 to 10, where A may be substituted with methyl, ethyl,propyl, phenyl or the like;

m is an integer of 1 to 10;

B is an alkylene group being methylene, ethylene, propylene, butylenes,pentylene, hexylene, heptylene, octylene or the like;

D is phenylene, pyridylene, pirimidylene, naphthylene, anthranylene,phenanthranylene, thiophenylene, furanylene or the like;

n is an integer of 2 to 5;

M is a monovalent metal cations, e.g., sodium, potassium and lithium ora polyvalent metal cation such as magnesium, calcium, nickel and iron.When M is a polyvalent metal cation, it forms an ion pair with 2 or moreCOO⁻ anions.

The repeating monomer unit represented by the general formula (5) ispreferably the one represented by the general formula (10):

wherein A is ethylene or propylene; m is an integer of 0 to 5, and whenm is 2 or more, A may be different at each occurrence; B is a singlebond or alkylene of 1 to 5 carbon atoms; D is phenylene or naphthylene;n is an integer of 2 to 5, and when n is 2 or more, D may be differentat each occurrence; and M is a mono- or polyvalent metal cation.

The polymer compound comprising the monomer units represented by thegeneral formula (5) can be produced by alkaline hydrolysis of theterminal ester segment of a polymer compound comprised of thecorresponding monomer unit represented by the general formula (4). Itmay be also produced by acid hydrolysis followed by alkali treatment.However, the former process is more preferable.

The polymer compound comprising monomer units represented by the generalformula (5) has a number-average molecular weight of 200 to 10,000,000,preferably 1000 to 1,000,000. Those having a molecular weight above10,000,000 may not be readily dispersed in a solvent, because ofexcessive entanglement within or between the polymer chains, and thoseof a molecular weight below 200 may not exhibit full steric effect of apolymer compound due to too small molecular weight. The polymer compoundof the present invention may be a homopolymer comprising a singlemonomer unit or copolymer comprising two or more monomer units. In thecase of copolymer, it contains a monomer unit represented by the generalformula (5) preferably at 1% by mole or more, more preferably 3% by moleor more. When the content of the monomer unit represented by the generalformula (5) is lower than 1% by mole, functions such as dispersionimprovement may not be satisfactorily exhibited. Preferably, thecopolymer contains vinyl ether monomer units 50% by mole or more of themonomer units, more preferably 80% by mole or more.

The polymer compound of each of the fifth and sixth aspects of thepresent invention is suitably used as a component for a composition ofthe first aspect of the present invention.

<Polymer Compound of the Seventh Aspect>

The seventh aspect of the present invention is the block polymercompound having a monomer unit represented by the general formula (1).

In the general formula (1) representing the monomer unit contained inthe block polymer compound of the present invention, carbon number of A,the preferable ranges of m and n, and specific examples of A, B, D and Rare the same as those in the general formula (1) for the polymercompound of the first aspect.

More specifically, in the general formula (1), A as an alkylene grouppreferably has a carbon number of 2 to 10. The alkylene group as A maybe substituted with methyl, ethyl, propyl, phenyl or the like.

m is an integer preferably of 1 to 10.

B as an alkylene group is methylene, ethylene, propylene, butylenes,pentylene, hexylene, heptylene, octylene or the like.

D as an aromatic ring structure is phenylene, pyridylene, pirimidylene,naphthylene, anthranylene, phenanthranylene, thiophenylene, furanyleneor the like.

n is an integer preferably of 1 to 5.

R as an alkyl group preferably has a carbon number of 1 to 10. R as anaromatic ring structure is phenyl, pyridyl, biphenyl group or the like.It may be substituted with an alkyl, alkoxy group, or the like.

The preferable monomer unit represented by the general formula (6) isthe preferable one included in the block polymer of the presentinvention.

The specific examples of the repeating monomer unit represented by thegeneral formula (1) are also the specific ones for the block polymercompound of the present invention.

The block polymer compound can be produced preferably by polymerizationof the polymerizable compound represented by the general formula (3).This process is mainly effected by cationic polymerization in thepresence of a polymerization initiator. The polymerization initiatorsuseful for the above process include protonic acids, e.g., hydrochloric,sulfuric, methanesulfonic, trifluoroacetic, trifluoromethanesulfonic andperchloric acid; and combinations of Lewis acid (e.g., BF₃, AlCl₃,TiCl₄, SnCl₄, FeCl₃, RAlCl₂ or R_(1.5)AlCl_(1.5), where R is an alkyl)and cation source (e.g., protonic acid and water, alcohol or adduct ofvinyl ether and carboxylic acid). The polymer compound can be producedby the polymerization of the polymerizable compound (monomer)represented by the general formula (3) proceeding in the presence of thepolymerization initiator.

Next, the polymerization process more suitably used for the presentinvention is described. A number of processes have been proposed forproduction of polymers comprised of polyvinyl ether monomer units (e.g.,Patent Document 10). Representative one is cation living polymerizationproposed by Aoshima et al (Patent Documents 11 and 12). Cation livingpolymerization can produce various polymers with a precise length(molecular weight), and these polymers include homopolymers, copolymerscomprised of plural monomer components, block polymers, graft polymersand graduation polymers. Alternatively, living polymerization processcan be carried out using HI/I₂ or HCl/SnCl₄.

The block polymer compound of the seventh aspect has a block segmentcomprised of monomer units represented by the general formula (1), andat least one block segment different from the above segment.

The monomer unit constituting the block segment different from thatrepresented by the general formula (1) is preferably represented by thegeneral formula (11):

wherein R¹ is selected from the group consisting of a straight, branchedor cyclic alkyl group of 1 to 18 carbon atoms, Ph, Pyr, Ph-Ph, Ph-Pyr,—(CH(R²)—CH(R³)-O)_(p)-R⁴ and —(CH₂)m-(O)_(n)-R⁴, where the aromaticring may be substituted with a straight or branched alkyl group of 1 to4 carbon atoms, and carbon atom in the aromatic ring may be replaced bynitrogen atom;

p is an integer of 1 to 18, m is an integer of 1 to 36, and n is 0 or 1;

R² and R³ are each independently a hydrogen atom or CH₃;

R⁴ is selected from the group consisting of hydrogen atom, a straight,branched or cyclic alkyl group of 1 to 18 carbon atoms, Ph, Pyr, Ph-Ph,Ph-Pyr, —CHO, —CO—CH═CH₂, —CO—C(CH₃)═CH₂ and —CH₂COOR⁷, and when R⁴ isother than hydrogen atom, the hydrogen atom bound to the carbon atom maybe replaced by a straight-chain or branched alkyl group of 1 to 4 carbonatoms, or F, Cl or Br, and the carbon atom in the aromatic ring may bereplaced by nitrogen atom;

R⁷ is hydrogen atom, or an alkyl group of 1 to 4 carbon atoms; and

Ph is phenyl group, and Pyr is pyridyl group.

More specifically, these monomer units include:

The block polymer of the present invention contains the monomer unitsrepresented by the general formula (1) 0.01 to 99.5% by mole of thepolymer compound, preferably 1 to 95%. If the content is lower than0.01%, it may have an insufficient interaction on the polymer compound,above 99.5%, it may exhibit its function insufficiently, because of theexcessive interaction conversely. The monomer units other than thoserepresented by the general formula (1) are incorporated at 0.5 to 99.99%by mole of the polymer compound, preferably 5 to 99%.

The block polymer compound comprising monomer units represented by thegeneral formula (1) has a number-average molecular weight (Mn) of 200 to10,000,000, preferably 1000 to 1,000,000. The compound having amolecular weight above 10,000,000 may not be readily dispersed in asolvent, because of excessive entanglement within or between the polymerchains. On the other hand, those having a molecular weight below 200 maybe difficult to fully exhibit the steric effect as a polymer compound,because of excessively low molecular weight.

<Block Polymer Compound of the Eighth Aspect>

The eighth aspect of the present invention is a block polymer compoundcomprised of monomer units represented by the general formula (2).

In the general formula (2) representing the monomer unit contained inthe block polymer compound of the present invention, the preferable A,m, B, D, n, M, and their specific examples are the same as described forthe second aspect above.

Specific examples of the monomer units represented by the generalformula (2) in the second aspect of the present inventions are alsothose of the monomer units for the block polymer of the presentinvention.

The block polymer compound having a monomer unit represented by thegeneral formula (2) can be produced by alkali hydrolysis of the terminalester segment of a polymer compound comprised of corresponding monomerunits represented by the general formula (1). It may be also produced byacid hydrolysis, followed by alkali treatment. However, the formerprocess is more preferable. It may be also produced by hydrolysis in thepresence of an alkali, followed by cation exchanging.

The polymer compound of the eighth aspect has a block segment, and atleast one block segment having a structure different from that of theformer. The monomer units constituting the block segment different fromthat represented by the general formula (2) is preferably represented bythe general formula (11).

The monomer unit represented by the general formula (2) to be containedin the block polymer compound of the present invention is incorporatedat 0.01 to 99.5% by mole of the whole polymer compound, preferably 1 to95%. Its content beyond the above range is not desirable; it may have aninsufficient interaction on the polymer compound when present at below0.01%, and may exhibit its function insufficiently when present at above99.5% because of the excessive interaction conversely. The monomer unitother than that represented by the general formula (2) is incorporatedat 0.5 to 99.99% by mole of the whole polymer compound, preferably 5 to99%.

The block polymer compound comprising monomer units represented by thegeneral formula (2) has a number-average molecular weight (Mn) of 200 to10,000,000, preferably 1000 to 1,000,000. The compound having amolecular weight above 10,000,000 may not be readily dispersed in asolvent, because of excessive entanglement within or between the polymerchains. On the other hand, those having a molecular weight below 200 maybe difficult to fully exhibit the steric effect as a polymer compound,because of excessively low molecular weight.

One of the favorable properties which the block polymer compounds of theseventh and eighth aspects are expected to exhibit is an amphipathicproperty. This property can be realized by providing the compound withhydrophobic and hydrophilic block segments simultaneously. The blockpolymer compound of the present invention can form a micellar conditionin an aqueous solvent, when it is amphipathic. In such a case, theamphipathic polymer compound has properties desirable properties forrecording materials, which is discussed later.

For improved dispersion stability and inclusion capacity, it ispreferable for the block polymer to have more flexible molecular motionin view of entanglement and affinity with the functional material.Flexible block polymers are also preferable because it can easily form acoating layer on a recording medium, as discussed later. For thisreason, glass transition temperature Tg of the main chain of the blockpolymer is preferably 20° C. or lower, more preferably 0° C. or lower,still more preferably −20° C. or lower. Generally speaking, polyvinylether polymers have a low Tg and flexibility. Most of the above monomerunits have a glass transition temperature of around −20° C. or lower.

The polymer compounds of the fifth and sixth aspects of the presentinvention, and block polymer compounds of the seventh and eighth aspectsare each the preferable component for the composition of the firstaspect of the present invention.

Each segment in the block polymer compound may be composed of a singlemonomer unit, or 2 or more monomer units. Moreover, the block polymercompound of the present invention may be a di-, tri- or tetra-blockpolymer or higher. It may be also a block polymer graft-bonded toanother polymer.

<Block Polymer Compound of the Ninth Aspect>

The block polymer compound of the present invention is characterized byhaving an aromatic carboxylic acid structure. One of the characteristicsof an aromatic carboxylic acid is a high acidity in comparison withcarbolic acid, or aliphatic carboxylic acids, that is, it has a lowerpKa representing acidity. This means that dissociation degree ofaromatic carboxylic acid or its alkali salt is high. As such, it canrealize a block polymer having high amphipathic properties, which candisperse functional material and stabilize the dispersion efficiently.

The block polymer of the present invention can be an organic acid andits alkali salt having a pKa value of 4.5 or less, more preferably 4.3or less. Thus, due to its high dissociation degree, it realizes a blockpolymer having high amphipathic properties, as well as higherdispersibility and dispersion stability of a functional material. pKavalue is a dissociation index of an acid. pKa can be determined from itsconcentration and hydrogen ion concentration in water as describedbelow.

In the present invention, when pKa of a polymer is determined, theconcentration is mole concentration of the monomer units having acidicfunctional group, not the mole concentration of the polymer. The moleconcentration of the monomer units can be determined by acid-basetitration, or by NMR analysis.

In a dilute aqueous solution, acid dissociation constant Ka isrepresented by [H₃O⁺][B⁻]/[BH], where BH is an organic acid, B⁻ is theconjugate base of the organic acid. pKa is −logKa.

pKa can be determined by using hydrogen ion concentration measured by apH meter and the above-defined mole concentration.

As described above, the present invention provides a polymer compoundwhich is suitably used to prepare an ink or a toner composition bydispersing a colorant or solid component more efficiently. Thecomposition of the present invention is suitably used for variousimage-forming methods, e.g., electrophotography and ink-jet printing.

Moreover, the polymer compound of the present invention, with a solventor dispersion medium, can provide compositions of the present invention,e.g., ink or toner compositions, and recording materials.

The present invention is described in more detail by EXAMPLES, which byno means limit the present invention.

EXAMPLE 1 Synthesis of

A mixture of 0.8 mols of potassium carbonate, 0.42 mols of ethyl4-hydroxybenzoate and 4 g of tetrabutyl ammonium iodide in 300 mLethanol and 0.42 mols of 2-chloroethyl vinyl ether was heated underreflux for 40 hours in a nitrogen atmosphere. The reaction mixture wasfiltered, distilled to remove the solvent, then applied to columnchromatography, and recrystallized from methanol. This produced

99.9% pure as determined by gas chromatography, in a yield of 32%.

The compound prepared in EXAMPLE 1 was hydrolyzed, and the resultantcarboxylic acid had a pKa value of 4.38 in water.

EXAMPLE 2 Synthesis of Polymer Compound (1)

0.1 mols of the polymerizable compound prepared in EXAMPLE 1, 0.001 molsof water and 0.005 mols of ethyl aluminum dichloride were reacted bycationic polymerization in anhydrous toluene.

The reaction was allowed to proceed for 20 hours, and then stoppedadding methylene chloride and water to the reaction mixture. The mixturewas washed with water, with dilute hydrochloric acid and then with analkali, dried on anhydrous sodium sulfate, and distilled to remove thesolvent, to produce a high molecular weight compound (polymer). It had anumber-average molecular weight of 4,100, determined by volume exclusionchromatography.

EXAMPLE 3

Synthesis of

was prepared in the same manner as in EXAMPLE 1, except that ethyl4-hydroxybenzoate was replaced by CH₂═CHOCH₂CH₂OCH₂CH₂OTs (Ts is tosylgroup) (yield: 21%).

EXAMPLE 4

Synthesis of

was prepared in the same manner as in EXAMPLE 1, except that ethyl4-hydroxybenzoate was replaced by ethyl 4-(4′-hydroxyphenyl)benzoate(yield: 22%).

The polymerizable compound prepared in each of EXAMPLES 3 and 4 waspolymerized in a manner similar to that for EXAMPLE 2, to prepare thepolymer compound. These compounds had number-average molecular weightsof 1,800 and 3,400, respectively, determined by volume exclusionchromatography.

EXAMPLE 5 Synthesis of Polymer Compound (2)

The polymer compound prepared in EXAMPLE 2 was stirred with a 5N aqueoussolution of sodium hydroxide at room temperature (23° C.) for 40 hoursto hydrolyze the ester. The reaction mixture was neutralized with 5Nhydrochloric acid, extracted with methylene chloride, dried, distilledto remove the solvent so as to obtain free carboxylic acid polymer.Neutralized with the same amount of 1N sodium hydroxide and distilled toremove water, sodium carboxyl ate salt polymer was obtained.

EXAMPLE 6 Production of Ink Composition (1)

Three parts of pigment (Cabot's Mogul L), 5 parts of the polymercompound prepared in EXAMPLE 2 and 15 parts of diethylene glycol weredispersed in 77 parts of ion-exchanged water by an ultrasonichomogenizer, all parts by weight. The resulting dispersion was filteredthrough a 1 μm filter under pressure, to prepare an ink composition. Thepigment was found well dispersed.

EXAMPLE 7 Production of Ink Composition (2)

Three parts of pigment (Cabot's Mogul L), 5 parts of the sodiumcarboxylate salt type polymer prepared in EXAMPLE 5 and 15 parts ofdiethylene glycol were dispersed in 79 parts of ion-exchanged waterusing an ultrasonic homogenizer, all parts by weight. The resultingdispersion was filtered through a filter of 1 μm pore size underpressure, to prepare an ink composition. The pigment was found welldispersed.

EXAMPLE 8 Printing Test (1)

The ink-jet printing test was carried out using the ink compositionprepared in EXAMPLE 7. Normal paper was printed with this inkcomposition by an ink jet printer (Canon's Bubble Jet Printer BJF800).The fine, black letters were printed.

EXAMPLE 9 Production of Toner Composition (1)

The free carboxylic acid polymer as the precursor for the sodiumcarboxylate polymer prepared in EXAMPLE 5 was used to prepare a tonercomposition by the following procedure.

100 parts of a polyester resin (synthesized from bisphenol A,terephthalic acid, n-dedecenylsuccinic acid, trimellitic acid anddiethylene glycol in a molar ratio of 20:38:10:5:27), 70 parts ofmagnetite (Fe₃O₄), 3 parts of the free carboxylic acid polymer describedabove, 2 parts of triphenylmethane-based dye and 3 parts of alow-molecular weight polypropylene, all parts by weight, werepreliminarily mixed, and then molten/kneaded by an extruder. The mixturewas cooled, roughly divided by a speed mill, finely divided by a jetmill and classified by a zigzag classifier, to produce a toner having avolume-average diameter of 11 μm.

100 parts of the toner was mixed with 0.4 parts of positivelychargeable, hydrophobic, dry type silica, treated with an amino-modifiedsilicone oil (viscosity: 100 cp at 25° C. and amine equivalents: 800)and 0.2 parts of spherical PVDF particles (average particle diameter:0.2 μm) by a Henschel mixer, all parts by weight, to prepare apositively chargeable toner composition. The toner composition gave afine copy on a copier (Canon's copier NP-3525).

<Synthesis of Block Polymer Compound and Production of Composition>

In EXAMPLES 10 to 18, the polymerizable compound prepared in EXAMPLE 1is referred to as Monomer B.

EXAMPLE 10 Synthesis of AB Block Polymer Compound of Isobutyl VinylEther (IBVE: Block Component A) and Monomer B

(Block Component B)

A glass container equipped with a stop cock was purged with nitrogen,and heated at 250° C. to remove adsorbed water. The container was cooledto room temperature, and charged with 12 mmols of IBVE, 16 mmols ofethyl acetate, 0.05 mmols of 1-isobutoxyethyl acetate and 11 mL oftoluene. The reaction was cooled, to which 0.2 mmols of ethyl aluminumsesqui-chloride (equimolar mixture of diethyl aluminum chloride andethyl aluminum dichloride) was added at 0° C. to initiate thepolymerization to synthesize the component A for the AB block polymer.Molecular weight of the component A (IBVE) was monitored periodically bymolecular-sieve column chromatography (GPC) to determine completion ofthe polymerization.

Then a toluene solution containing 10 mmols of Monomer B (blockcomponent B) was added to the reaction, and the polymerization wascontinued for 20 hours and then stopped by adding an aqueous solution of0.3% by weight of ammonia/methanol. The reaction mixture was dilutedwith dichloromethane, and washed 3 times with 0.6M hydrochloric acid andthen 3 times with distilled water. The resulting organic phase wasconcentrated to dryness on an evaporator, dried under a vacuum, anddialyzed repeatedly through a semi-permeable membrane of cellulose in amethanol solvent to remove the monomer compound, to prepare a diblockpolymer as the target product. The polymerization ratio A/B was 100/28.The compound was identified by NMR and GPC. It had an Mn value of 30,700and Mw/Mn ratio of 1.38.

EXAMPLE 11

The block polymer compound prepared in EXAMPLE 10 was hydrolyzed in amixed aqueous solution of dimethylformamide and sodium hydroxide. As aresult, side chains of the block component B were hydrolyzed, yielding adiblock polymer sodium salt. The compound was identified by NMR and GPC.

It was further neutralized with 0.1N hydrochloric acid in a waterdispersion to have the component B converted into free carboxyl group.The compound was identified by NMR and GPC.

The carboxylic acid segment in the above block polymer had a pKa valueof 4.29 in water.

EXAMPLE 12 Synthesis of Block Polymer (2)

A block polymer was prepared in the same manner as in EXAMPLE 10, exceptthat IBVE as the component B for the block polymer was replaced by2-ethoxyethyl vinyl ether. Its polymerization ratio A/B was 100/29. Ithad an Mn value of 28,700 and Mw/Mn ratio of 1.45.

EXAMPLE 13 Production of Ink Composition (3)

3 parts of a black-color pigment (Cabot's Mogul L), 4 parts of thesodium salt type block polymer prepared in EXAMPLE 11 and 15 parts ofdiethylene glycol were dispersed in 78 parts of ion-exchanged water byan ultrasonic homogenizer, all parts by weight. The resulting dispersionwas filtered through a 1 μm filter under pressure, to prepare an inkcomposition. The pigment was found well dispersed.

EXAMPLE 14 Print Test (2)

The ink-jet printing test was carried out using the ink compositionprepared in EXAMPLE 13, where a common paper was printed with the inkcomposition prepared in EXAMPLE 13 by an ink jet printer (Canon's BubbleJet Printer BJF800), whose ink tank was filled with the composition. Thefine, black letters were printed.

EXAMPLE 15 Production of Toner Composition (2)

The diblock polymer of free carboxylic acid form prepared in EXAMPLE 11was used to prepare a toner composition by the following procedure. 100parts of a polyester resin (synthesized from bisphenol A, terephthalicacid, n-dedecenylsuccinic acid, trimellitic acid and diethylene glycolin a molar ratio of 20:38:10:5:27), 70 parts of magnetite (Fe₃O₄), 3parts of the free carboxylic acid polymer prepared in EXAMPLE 11, 2parts of triphenylmethane dye and 3 parts of a low-molecular weightpolypropylene, all parts by weight, were preliminarily mixed, and thenmolten/kneaded by an extruder. The mixture was cooled, roughly dividedby a speed mill, finely pulverized by a jet mill and classified by azigzag classifier, to produce a toner having a volume-average diameterof 11 μm.

100 parts of the toner was mixed with 0.4 parts of positivelychargeable, hydrophobic, dry type silica that had been treated with anamino-modified silicone oil (viscosity: 100 cp at 25° C. and amineequivalents: 800) and 0.2 parts of spherical PVDF particles (averageparticle diameter: 0.2 μm) by a Henschel mixer, all parts by weight, toprepare a positively-chargeable toner composition. The toner compositiongave a fine, black-colored copy using a copier (Canon's productNP-3525).

EXAMPLE 16 Production of Ink Composition (4)

26 parts of the diblock polymer of free carboxylic form prepared inEXAMPLE 11 and 10 parts of an oil-soluble dye (Oil Blue N, Aldrich) wereco-dissolved in dimethylformamide, and the solution was turned into anaqueous phase with 400 parts of distilled water, all parts by weight, toprepare an ink composition. The Oil Blue component was not separated orprecipitated, when the ink composition was left to stand for 10 days.

The diblock polymer prepared in EXAMPLE 12 was hydrolyzed in a mannersimilar to that in EXAMPLE 11 to prepare a block polymer of carboxylicacid salt form. 26 parts of the block polymer and 10 parts of anoil-soluble dye (Aldrich's Oil Blue N) were co-dissolved indimethylformamide, and the solution was turned into an aqueous phasewith 400 parts of distilled water, all parts by weight, to prepare anink composition in the same manner as in EXAMPLE 16. It is known thatthe poly-2-ethoxyethyl vinyl ether segment being the hydrophobic segmentof the compound becomes hydrophilic at low temperature. When thecompound was cooled to 0° C., the oil-soluble dye (Oil Blue) separatedout, indicating that the dye had been included in the polymer micelles.

EXAMPLE 17 Thickening

The dispersion of micelles holding the oil-soluble dye, prepared inEXAMPLE 16, was treated with 2N hydrochloric acid to be pH 3. As aresult, the composition became greatly viscous to have a viscosity of0.250 Pas (250 cps). When the same printing test was carried out as inEXAMPLE 8 on normal paper sprayed with hydrochloric acid, fine printswere obtained. When these prints were rubbed with a line marker, no bluetailing was observed, proving good fixability and water resistance ofthe print.

EXAMPLE 18

A diblock polymer compound was prepared in the same manner as in EXAMPLE10, except that Monomer B was replaced by a monomer having a structurerepresented by

A composition was prepared in the same manner as in EXAMPLE 13 using theabove polymer, and print test by ink-jet system was carried out also inthe same manner as in EXAMPLE 8. The fine prints were obtained.

COMPARATIVE EXAMPLE

An ink composition was prepared using styrene-sodium acrylate copolymer(polymerization ratio: 100/30, number-average molecular weight: 33,000)in the same manner as in EXAMPLE 13. The printing test was also carriedout in the same manner as in EXAMPLE 8 using a BJF800 printer, whose inktank was filled with the composition. It could not be discharged fromthe printer, and no print was obtained.

1. A composition comprising a polymer compound and a medium being asolvent or a binder resin, the polymer compound comprising a monomerunit represented by the general formula (1):

wherein A is a straight-chain or branched alkylene group of 1 to 15carbon atoms with or without substitution; m is an integer of 0 to 30,and when m is 2 or more, A is the same or different each other; B is asingle bond or an alkylene with or without substitution; D is anaromatic ring structure; n is an integer of 1 to 10, and when n is 2 ormore, D is the same or different with each other; and R is a hydrogenatom, an alkyl group with or without substitution, or an aromatic ringstructure with or without substitution; or a monomer unit represented bythe general formula (2)

wherein A is a straight-chain or branched alkylene group of 1 to 15carbon atoms with or without substitution; m is an integer of 0 to 30,and when m is 2 or more, A is the same or different from each other; Bis a single bond or alkylene with or without substitution; D is anaromatic ring structure; n is an integer of 1 to 10, and when n is 2 ormore, D is the same or different from each other; and M is a mono- orpoly-valent metal cation.
 2. The composition according to claim 1,wherein said polymer compound is a block polymer compound.
 3. Thecomposition according to claim 2, wherein said block polymer compound isamphipathic.
 4. The composition according to claim 3, wherein the mediumis a solvent, and said polymer compound forms a micelle in said solvent.5. A recording material comprising a composition of claim 1 and acolorant.
 6. The recording material according to claim 5, wherein therecording material is a toner composition and the medium is a binderresin.
 7. The recording material according to claim 5, wherein therecording material is an ink composition, and the medium is a solvent.8. A recording method using a recording material according to claim 5,comprising a step of bringing a hydrogen ion or metal cation in contactwith said composition for thickening.
 9. An image-forming method using arecording material according to claim 7, wherein said ink composition isapplied by ink-jet recording on a recording medium.
 10. A block polymercompound comprising a monomer unit being an organic acid or a saltthereof, wherein the block polymer compound has a main chain ofpolyvinyl ether and pKa of 4.50 or less.
 11. A composition comprising ablock polymer compound according to claim 10 and a solvent or a binderresin.
 12. A recording material comprising a composition according toclaim 11 and a colorant.
 13. A composition comprising a block polymercompound and a solvent or a binder resin, wherein the block polymercomprises a polyvinyl ether monomer unit selected from the groupconsisting of carboxylate ester, carboxylic acid and carboxylic acidsalt.
 14. A recording material comprising a composition according toclaim 13, and a coloring material.
 15. A polymerizable compoundrepresented by the general formula (3):CH₂═CHO(AO)_(m)B(D)_(n)COOR wherein A is a straight-chain or branchedalkylene group of 1 to 15 carbon atoms with or without substitution; mis an integer of 0 to 30, and when m is 2 or more, A is the same ordifferent from each other; B is a single bond or alkylene with orwithout substitution; D is an aromatic ring structure; n is an integerof 2 to 10, and D is the same or different from each other; and R is ahydrogen atom, an alkyl group with or without substitution, or anaromatic ring structure with or without substitution.
 16. A polymercompound comprising a monomer unit represented by the general formula(4):

wherein A is a straight-chain or branched alkylene group of 1 to 15carbon atoms with or without substitution; m is an integer of 0 to 30,and when m is 2 or more, A is the same or different from each other; Bis a single bond or alkylene with or without substitution; D is anaromatic ring structure; n is an integer of 2 to 10, and D is the sameor different from each other; and R is a hydrogen atom, an alkyl groupwith or without substitution, or an aromatic ring structure with orwithout substitution. 17-21. (canceled)